Triamino-s-triazines

ABSTRACT

THE COMPOSITIONS DISLOSED HEREIN COMPRISE DERIVATIVES OF SYMMETRICAL TRIAZINES IN WHICH AT LEAST ONE OF THE DERIVATIVE GROUPS HAS A RADICAL OF THE FORMULA   -CHR4COOM   WHEREIN M IS HYDROGEN, A QUATERNARY AMMONIUM GROUP OR METAL, AND R4 REPRESENTS HYDROGEN, PHYENYL, CYCLOHEPTYL, CYCLOHEXYL OR AN ALKYL GROUP OF 1-6 CARBON ATOMS. THESE COMPOUNDS ARE USEFUL FOR CHELATING OR COORDINATING METAL IONS AND RECOVERY OF THE SAME FROM SOLUTIONS.

United States Patent 3,637,685 TRIAMINO-s-TRIAZINES Gaetano F. DAlelio,South Bend, Ind., assignor of a fractional part interest to Walter J.Monacelli, Cleveland, Ohio No Drawing. Filed May 15, 1967, Ser. No.638,654 Int. Cl. C07d 55/24 US. Cl. 260-249.6 5 Claims ABSTRACT OF THEDISCLOSURE The compositions disclosed herein comprise derivatives ofsymmetrical triazines in which at least one of the derivative groups hasa radical of the formula CHR COOM wherein M is hydrogen, a quaternaryammonium group or metal, and R represents hydrogen, phenyl, cycloheptyl,cyclohexyl or an alkyl group of l-6 carbon atoms. These compounds areuseful for chelating or coordinating metal ions and recovery of the samefrom solutions.

This invention relates to new chemical compounds and more particularlyto triazine derivatives. The invention is concerned especially with theproduction and use of new and useful triazines having the property ofcoordinating metal ions.

The chemical compounds of this invention may be represented by thegeneral formula,

wherein at least one of said valencies is attached to a T group.

In the above triazine formula, Y can be R which represents hydrogen orany monovalent hydrocarbon radical, whether saturated or unsaturated,substituted or unsubstituted, aliphatic, carbocyclic, aryl orheterocyclic, monoor polynuclear, etc. Examples of suitable hydrocarbongroups represented by R are aliphatic, aromatic, e.g., methyl, ethyl,propyl, isopropyl, butyl, secondary butyl, butenyl, amyl, hexyl, allyl,methallyl, cyclopentenyl, cyclohexyl, cyclohexenyl, phenyl, diphenyl,naphthyl, tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl,allylphenyl, benzyl, phenylallyl, phenylpropyl, etc., and theirhomologues, as well as those groups with one or more of their hydrogenatoms substituted by halogens, as, for example, fluorine, chlorine,nitro groups, nitroso groups, amino groups, carboxy groups.

T represents a grouping of atoms having a chelating or coordinationfunction with metal ions, that is, T contains functional groups capableof forming complexes with metal salts through covalent linkages ratherthan through electrovalent linkages.

The essential difference between the ordinary electro- 3,637,685Patented Jan. 25, 1972 ice valent bond and the covalent bonds in thecoordination compounds may be demonstrated by comparing nonpolymericmolecules containing such bonds. The bond in the former is ionic andsimilar to those that exist in such compounds as sodium phosphate,copper acetate, nickel sulfate, aluminum nitrate and many other salts.The bonds in the latter metals such as chromium, iron, cobalt,molybdenum, uranium, nickel, copper, zinc platinum, mercury, gold,silver, titanium, zirconium, vanadium, etc. A typical example of such acoordination compound is hexamine-cobalt(III) chloride, whose formula is[CO(NH ]Cl this compound is prepared by reacting cobaltic chloride, C001which has its ionic valencies satisfied, with six (6) moles of ammoniawhereby the ammonia molecules are coordinated to the cobalt atom throughnon-ionic covalent linkages. Ethylenediamine will also complex withcobaltic chloride to give trisethylenediamine-cobalt(III) chlorideHzNCHz W )l HgNcHg 3 When the complexing compound, such asethylenediamine, can occupy simultaneously more than a singlecoordinating position, ring formation can occur and ring structures maybe found in the complex. Such ring compounds are known as chelatecompounds. The ring-forming groups are known as polydentate groups or aschelating groups, in contrast to the monodentate groups which maycoordinate without forming ring or chelate compounds.

A large number of organic compounds containing suitable substitutentgroups function as chelating compounds of which ethylenediamine,diethylenetriamine, etc., are typical examples. Another example is2,2-dipyridyl which complexes with ferrous chloride to give N Ft C12Other organic compounds which contain in their structure both saltforming groups and neutral donor groups can, through coordination orchelation, satisfy both the oxidation number of, and the coordinationnumber of many metal ions, a typical example of which is the copper(II)chelate of S-hydroxyquinoline,

Glycine and substituted glycines behave similarly as shown in copper(II)glycinate,

Accordingly, it is a proposal of this invention to attach T groups whichact as coordination groups to the triazine rings, in which the T groupsare selected from the class consisting of 3 and metals and R representsa radical selected from the class of H and a hydrocarbon radicalcontaining one to six carbon atoms. A few illustrative examples of the IIN 5 group are I -NHNHCH COOM; -NHN (CH COOM 2 can on, on ona 10 whereinR R R R have the same meaning as previously described hereinabove, and nrepresents an integer of one to six. A few typical examples of thesegroups are:

NH (CH N CHzCOOM etc.

wherein R R and R have the same meaning as described hereinabove, and Zis a divalent aromatic hydrocarbon radical containing six to twelvecarbon atoms. A few illustrative examples of these groups are:

-NHC H (CH N(CH COOM) NHC H (CH NHCH COOM NHC H NHCH COOM, etc.

R2 OCH R (CH R n N wherein R R R and n have the same meaning as definedhereinabove, and a few illustrative examples are: 60

r 0 CH CHgNHC C O OM etc.

wherein Z, R and R have the same meaning as defined hereinabove, a fewillustrative examples of which are:

In general, the triazine compounds used in the practice of thisinvention can be prepared conveniently by reacting in the presence of ahydrohalide acceptor, HAC, the corresponding halotriazines, for example,the bromoor chloro-triazines with the corresponding halotriazines, forexample the bromoor chloro-triazines with the corresponding TH compoundswherein T is as previously defined, and H is an active hydrogen attachedto the T group, e.g.,

HAG (CsNa) C1; 3TH (CaNa) (T):

HAG Y2(C3Na) C1 TH (Y)2(C3N3)T and some specific examples of the abovereactions are NaOH (NH2)2(CaNa) C1 NH2N(CH2COON8.)2

(NH2)2(C3N3) [NHN(CI-IzC 0 ONa)z] 2 NaOH NHz(C3Na)(Cl)2 2NHzN(CHzCOONa)2 NH2(C3N3) [NHN(CH2C 0 ONa) z]:

(CaNa) (NHNHCHzC O 0N3):

The present invention is based on the discovery that new and valuablematerials are obtained by having three T group of the type describedabove attached to the triazine ring. They can be used in the treatmentof water to coordinate metallic ions and to maintain the ions insolutions when water-solubilizing groups are attached to the triazinering, e.g.,

As such they are useful in laundering, chemical processing, etc. Theycan also be used in the preparation of stable pigments as for examplethe copper coordinate of (C N (NHNCH COOH) Z is a stable blue and thecobalt coordinate is a stable red. These coordinate-pigments are waterinsoluble, especially if to the triazine there is attached one or two Ygroups contributing to water insolubility, e.g.,

and [(C H N] 'C N NHN (CH COOM) and they become organophilic when Ycontains hydrocarbon groups such as and C H NHC N [OCH CH N(CH COOM) Thecompounds of this invention having suitable Y groups can be used also toprepare addition and condensation polymers which coordinate with metalions. One class of condensation polymers can be prepared when the Ygroup attached to the triazine ring is an aldehyde reactable group aspreviously described herein, such as in NH (C N NHN (CH COOM 2 byreaction with an aldehyde, including aldehydes, hydroxy aldehydes andaldehyde addition products, e.g., paraformaldehyde, aldol, glucose,dimethyl urea, the methylol melamines, etc., to prepare products havingutility as chelating resins for the isolation and separation of metalions from dilute or concentrated solutions, as well as utility in theplastics, coating and impregnating arts. As chelating resins they areparticularly useful in recovering the metals of the commonchelating-forming metals, such as Al, Ti, V, Si, Cr, Mn, Fe, Co, Ni, Cu,Zn, Ga, Ge, As, Y, Zr, Cb, Mo, Tc, Rn, Pl, Pd, Ag, Cd, In, Sn, 'Sb,Hf,Ta, W, Rh, Os,

(c NaflNHNHcHzCOONah Thus it may be seen that it is the intent of thisinvention to include in the compounds of this invention, triazmederivatives of the formula wherein at least one of the valencies isattached to a T group and at least one other valency is attached to apolymer.

Thus it may be seen that the Y groups may be any polymerizable group aswell as a non-polymerizable group,

and that thus the Y group itself may be a polymer or preformed polymer,and that the compounds of this invention can be classified assymmetrical triazines having the structure,

to which is attached at least one and no more than three T groups, inwhich the T groups are as defined hereinabove.

These coordination resins differ from the conventional ion-exchangeresins. The conventional ion-exchange resins are polymer matrices towhich are attached functional acidic, basic or salt groups which areelectrovalent in nature and the resin exchanges ions by means of thesegroups in a manner similar to normal acids, bases or salts. Thecoordination resins are polymer matrices to which are attachedfunctional groups capable of forming complexes with metal ions and metalsalts through covalent linkages whereby more stable molecules areproduced.

Coordination resins which contain in their structures substituents whichfunction through the concerted action of salt forming groups andcoordinating groups are sometimes considered as a special class ofion-exchange resins. However, it is well-known that the conventionalionexchange resins are incapable of recovering heavy metal ions fromsolution containing a higher concentration of alkaliand alkaline-earthions because such resins function solely by ion-exchange involvingelectrovalent bonds, and their performance is determined by mass actionlaws. This may be illustrated using a cation exchange resin as anexample. Such a resin contains a crosslinked polymer matrix to which areattached functional acidic groups; such polymers may be regarded asinsoluble acids. Undoubtedly, the most widely used ion-exchange resintoday is the cation resin described in my U.S. Pat. 2,366,007 (1944) andis a sulphonated styrene-divinyl benzene polymer which may berepresented by RSO H, wherein R is the polymer matrix and -SO H,represents the sulfonic acid groups attached to the benzene rings in thepolymer.

These polymers will form salts and will exchange its cations with theion in solution. Thus the sodium form of the ion-exchange resin may beused to soften hard water by exchanging its sodium ions for the calciumand magnesium ions in solution, and because the process is one of ionexchange, leak-through of the calcium or magnesium ions will occur muchbefore all of the sodium in the resin has been exchanged for the calciumor magnesium and the resin will have to be regenerated. The spent resinis regenerated using sodium chloride solutions which direct theequilibrium to reform the sodium salt of the polymer. From the foregoingit is obvious that the cation exchange resin would be incapable ofremoving small quantities of calcium or magnesium from solutionscontaining sodium chloride in higher concentrations than theconcentration of calcium or magnesium, or that they could remove smallquantities of cupric or other heavy metal ions from sodium chloridesolution. It has been shown experimentally that in a column, the sodiumsalt of these resins shows little or no ability to remove copper from a3% sodium chloride solution containing 250 parts per million of cupricion.

In contrast to this, the coordination resins of this inventioncontaining at least one T group per triazine ring, are able to removethe copper quantitatively from these sodium chloride solutions, and thecopper derivative of these coordination resins are not regenerated tothe sodium salt by sodium chloride. These results point to the utilityof these resins capable of complexing metal cations by coordinationswithout depending on ion-exchange phenomena, not only in research andthe recovery of metals from processing wastes or from dilute solution,or for the purification of medicinals, food and industrial products orfor the control of pollution but also for carrying out such process inthe presence of high concentration of alkaline and alkaline-earth saltssuch as sodium chloride, potassium chloride, calcium chloride, magnesiumchloride, etc., and for the separation of these heavy metal cations fromeach other.

These chelating resins, as is the case in ion-exchange resins can beprepared as small discreet particles in granular or head forms and inthese forms are used in columns or containers through which the solutioncontaining the metal ions to be recovered or exchanged is passed.Initially, at the beginning of the process the resin efliciency is highand high rates of flow can be used. As the capacity of the resin isdecreased its efficiency is decreased. Since, in the solid polymer, therate of the exchange or coordination reaction is diffusion-controlled,the functional groups in the inside of the mass of the polymer are notutilized efficiently unless the rate of the flow of the solution throughthe bed of polymer particles is sufficiently low. When the capacity ofthe polymer is exhausted or leakthrough occurs, the process isinterrupted and the resin regenerated.

The coordination resins of this invention can also be prepared in otherforms such as in open pore structures such as are obtained byimpregnating open-pore natural sponges or synthetic cellulose sponges orpolyurethane foams with the soluble, fusible condensation products andthereafter insolubilizing the condensation products in situ. Or they canbe prepared in the form of sheets or membranes by impregnating cellulosepulp or paper, cotton mats, wood pulp, fiber board, sawdust board,cotton in the form of mats, woven fabrics, etc., with the intermediatestage of the condensation resins and thereafter insolubilized in situ.Likewise porous ceramic beads, slabs, tubes, etc., derived from fusedalumina, silica, etc., can be impregnated with the soluble, fusiblecondensation products and cured in situ.

The coordination resins can also be prepared in filamentary form bycoating or impregnating fibers such as cotton, regenerated cellulose,polyvinyl alcohol, homoand copolymer fibers, etc., with the condensationresins of this invention and then insolubilizing the product in situ.The filamentary form of these new resins of this invention areparticularly useful in treating very dilute solutions of metals. In thetreatment of very dilute solution, the costly handling of large volumesof solution to recover small quantities of metal, which, together withthe high attrition loss of the granular polymer, makes the processuneconomical, as for example, to recover one part of copper from asolution containing 250 parts of copper per million, it is necessary toprocess 4000 pounds of the solution, whereas if the solution containsonly 100 parts of copper per million, then 10,000 pounds of solutionmust be treated. The use of the filamentary form eliminates some of theproblems associated with the conventional granular processes by (1)preparing and using insoluble coordination polymers in filamentary formrather than in the form of discrete particles or membranes and (2)contacting the solution with the coordination resin in filamentary form.A further improvement consists in contacting the solution containing themetal cations with a new surface of the filamentary coordination polymerbefore substantial exhaustion of the capacity of the coordinationpolymer occurs by advancing the filamentary polymer intermittently orcontinuously is desired or required. Furthermore, the solution may betreated in a batch process or in a continuous-flow system. Furtherimprovements and modifications of the process of this invention includethe continuous regeneration of the filamentary coordination resin aswell as a continuous cyclic system which comprises contacting thesolution of metal cations with the filamentary coordination polymer,regenerating the coordination polymer and recontacting a solutioncontaining the metal cations with the regenerated coordination polymer.

The filamentary form of the coordination polymers used in the practiceof this invention may be prepared and used in various forms dependingupon the particular use desired and economic considerations. They may beprepared as single solid continuous-filaments similar to the commercialmonofilament fishing lines of various diameters from about .005" to .05"or higher in diameter; or in smaller diameters, which may be braided,twisted or woven into soft, pliable multifilament lines of variousdiameters. They may also be used in the form of hollow lines to increasethe buoyancy of the filament, or in the form of a solid or hollowribbon. Where long lengths of the filamentary coordination polymers areto be used in the process of this invention, and where there is dangerof breakage due to the weight of unsupported polymer exceeding orapproaching the limit of the tensile strength of the coordinationpolymer, the polymer may be reinforced by use of a reinforcing core ofanother filament such as another fiber, strands of fibers, wire, strandsof wire or by forming a mixed, twisted, braided or woven filament withother reinforcing filaments. In other cases, the coordination polymermay be used as a coating on a core of fiber, fibers or wire. The choiceof the specific form depends on the methods used in preparing thefilamentary coordination polymer from the intermediate available as wellas the cost of the particular form prepared and the specific use made ofthe filamentary coordination polymer.

The behavior of the coordination groups in the compounds and resins ofthis invention is determined by their stability constants. Thus, when acoordinating group as illustrated by a mole of CHzCO ONa CH2C O ONareacts by contact with a solution containing a mole of copper chloride,CuCl the chelate structure 0112000 N---Uu lilo will form, and with asolution of a mole of nickel chloride, NiCl the structure OH: 0 o 0 N-Niwill form, and in another solution containing /2 mole of CuCl and /2mole of NiCl one-half mole of each of these chelate structures will beformed. On the other hand, if a coordinating group having a mole ofimino diacetic acid coordinating groups is reacted with a solutioncontaining one mole of copper chloride and one mole of nickel chloride,only the copper chelate will form because the stability constant of thecopper chelate (K is about 3.5 X 10 is greater than that of the nickelchelate (K is about 2.75 x 10 and, for the same reason, if thenickel-chelated polymer is immersed in a solution of copper ion, thenickel will be replaced by copper and nickel will go into solution, eventhough these metal chelates are not regenerated by alkali ions.

For the iminoacetic acid group the qualitative order of selectivity isThus, if a mole of each ion is in solution, seven moles of iminoaceticacid groups will be required on the polymer to react with the six heavymetal ions and they will be absorbed simultaneously if sufficientiminoacetic acid groups are in contact with the solution, but if onlyone mole of iminoacetic acid groups is in contact with the solution,then only the lead is removed, and if two moles of iminoacetic acid arein contact with the solution, then lead and copper are removed, and ifthree moles of iminoacetic acid groups are in contact with the solution,then lead, copper and iron are removed, and similarly for 4, 5, 6, etc.,number of metals.

In the triazine derivatives, the activity of a coordination group, suchas etc., depends on the manner the group is attached to the triazinering. For example, I have discovered that when such groups are attacheddirectly to the triazine ring, as in such compounds as (NH (C N )NHCHCOOH,

(C N (NHCH COOH) (C N (NCH COOH) the coordination tendency of theaminoacid nitrogen is greatly reduced and that the substituent groupfunctions more nearly as a carboxylic acid forming primarilyelectrovalent bonds; while the exact reason for this behavior is notthoroughly known, it may be explained on the basis that the basicity ofthe amino acid nitrogen has been greatly reduced by the attachment tothe carbon atom in the triazine ring. Whether or not this theoryexplains this phenomenon satisfactorily, I have now discovered that ifthe amino nitrogen of the amino acid is attached to the carbon atom of atriazine ring by means of another atom or group of atoms so as topreserve the basicity of the amino nitrogen of the amino acid, then thecoordination tendency of the amino acid is maintained. Accordinglytherefore, the T groups attached to the triazine ring are substitutedamino acids in which at least one amino group is basic. These propertiesare found in the T groups defined hereinabove having the generalformulas,

9 wherein R R R R Z and n are as defined hereinabove.

The following examples illustrate the practice of this invention and aregiven by way of illustration and not by limitation. Unless specificallyindicated otherwise, the parts and percentages are intended as parts byweight and percentages by weight, respectively.

EXAMPLE I A slurry of cyanuric chloride is prepared by running a thinstream of a hot solution of 184.4 g. of cyanuric chloride in 400 ml. ofacetone into 600 ml. of stirred mixture of ice and water (O-5 C.), and366 parts of NH NHCH COONa added and the temperature raised slowly to 450., followed by the addition of 166 parts of Na CO and the mixtureheated to reflux for two hours, cooled, acidified with dilute H 80 andcooled to 5 C.; the triazine is removed by filtration. The filtrate isevaporated to dryness and extracted with anhydrous ethyl alcohol torecover addition product and there is obtained an almost quantitativeyield of C N (NHNHCH C-OOH 3 which, on analysis for C, H and N givesvalues of 31.21% C, 4.45% H, and 36.28% N, which values are in goodagreement with the theoretical values for the compound.

EXAMPLE II The procedure of Example I is repeated using 576 parts of NHN(CH COONa) and there is obtained the compound (C3N3)[NHN(CH2cOOH) WhlChon analyses for C, H and N gives values of 34.61%, C, 4.04% H, and 24.2%N which values are in close agreement with the theoretical values forthe compound.

EXAMPLE III To 750 ml. of water there is added 163 parts of NH (C N C1(prepared by the procedure of J.A.'C.S. 73, 2981 (1951)) and 384 partsof NH N(CH COONa) and the mixture refluxed for two hours during whichtime a 5% NaOH solution was added at such a rate as to maintain thesolution neutral or slightly so as indicated by phenolphthaleinindicator in the solution. The triazine derivative is then isolated bythe procedure of Example I and there is obtained the compound NH C N [NHN (CH COOH) 2 EXAMPLE IV The procedure of Example III is repeated using144 parts of (NH (C N )CI prepared by the procedure of J.A.C.S., 73,2981 (1951), and 192 parts of NH N(CH COONa) and there is obtained thecompound (NH (C N )NHN(CH COOH) EXAMPLE V The procedure of Example IV isrepeated using 162 parts of (CH NH) C N CI (prepared by the proceduregiven in J.A.C.S., 73, 2981 (1951)) and there is obtained the compound,(CH NH) (C N )NHN(CH COOH) EXAMPLE VI The procedure of Example IV isrepeated using 270 parts of (NH (H NO SC H NH) (C N )Cl, prepared by themethod of J. Org. Chem., 24, 643 (1956), and J.A.C.S., 73, 2981 (1951)and there is obtained the compound (NH (H NO SC H NH) (C N NHN (CH COOH)2 EXAMPLE VII The procedure of Example 1V is repeated using 203 parts of(NH (NI-I CONHNH) (C N )Cl (prepared by 10 the method of US. Patent2,295,562) there is obtained the compound (NHz) (NH CONHNH) (C N NHN (CHCOOH 2 EXAMPLE VIII The procedure of Example III is repeated using 209parts of HOCH CH NH(C N )Cl prepared by the procedure of J.A.C.S., 73,2986 (1951), and there is obtained the compound HOCH CH NH (C N [NHN (CHCOOH 2 EXAMPLE IX The procedure of Example IV is repeated using 233parts of (HOCH CH NH) C N Cl prepared by the procedure of J.A.C.S., 73,2986 (1951), and there is obtained the compound (HOCH CH NH C N NHN (CHCOOH) 2 EXAMPLE X The procedure of Example III is repeated using 344parts of (HOCH CH N(C N )(Cl prepared by the procedure of J.A.C.S., 73,2986 (1951), and there is obtained the compound (HOCH CH N (C N [NHN (CHCOOH 2 EXAMPLE XI The procedure of Example IV is repeated using 285parts of (NaOOCCH NH) C N Cl (prepared by the procedure of J. Org.Chem., 24, 643 (1959)) and there is obtained the compound (HOOCCH NH 2(C N NHN (CH COOH 2 EXAMPLE XII The procedure of Example III is repeatedusing 267 parts of CH CHC H NH(C N )Cl (prepared by the procedure ofJ.A.C.S., 73, 2981 (1951)) using The procedure of Example IV is repeatedusing 330 parts of (CH =CHC H NH) (C -N )Cl (prepared by the proceduregiven in J.A.C.S., 73, 2986 (1951)) and there is obtained the product(CH =CHC H NH) (C N NHN (CH COOH 2 EXAMPLE XIV The procedure of ExampleIII is repeated using 269 parts of CH CHC I-I O(C N )Cl (prepared fromusing the procedure of J.A.C.S., 73, 2989 (1951)), and there is obtainedthe compound When the procedure of Example IV is repeated using 334parts of (CH CHC H O) (C N )CI, there is obtained the compound CH =CHC HO 2 (C N NHN (CH COOH 2 EXAMPLE XV The procedure of Example IV isrepeated using 227 parts of (CH CHCH O) (C N )CI (prepared from CH CHCHOH and (C N )Cl according to J.A.C.S., 73, 2988 (1951)), and there isobtained the compound (CH CHCH O) C N NH-N (CH COOH 2 11 12 EXAMPLE XVIEXAMPLE XX The procedure of Example IV is repeated using 311 A slurry of368 g. of cyanuric chloride in 800 ml. of

parts of (CH CHCH OOCCH O) C N Cl (prepared acetone and 1200 ml. ofWater are reacted with 440 parts from HOCH COOCH H CH CH according to I.A.C.S. of

5 73, 2988 (1951)) and there 1s obtalned the compound (NH2)(SOSNa)C6H3CH:cHC6H3(SO3Na) (NHZ) (CH=**CHCHZOOCCHZ)2(C3N3)NHN(CH2COOH)2and 106 parts of Na CO at 10-1s c. There is obtained EXAMPLE XVII theintermediate in theoretical yield, The procedure of Example II isrepeated at 5 C. using 384 g. of N1I2N(cH2cooNa)2 184 g. of cyanuricchlo- CMCQNQNL ride in acetone, and 106 g. of Na CO and there is obltained the compound Cl(C N )[NHN(CH COONa) S031 S031 Then there is added376 parts of H(OCH CH OH One half of this compound is reacted with 384g. of and 40 g. of NaOH; the mixture refluxed for one hour NH N(CHCOONa) according to the procedure of EX- and there is obtained asolution of the compound ample III, and there is obtained the compound[(HOOC CH2) 29111111 03113 NH CH=CHNH(C1N3)[NHN(CH1COOH) SOzNa SO2N8which showed marked fluorescent properties. The other H(OCH2CH2)8O(C3N3)[NHNwHzcooNah half of this compound is first reacted With ammonia byEXAMPLE XVIII the procedure of I.A.C.S., 73, 2981 (1951) and thenExample XVII is repeated to form the with 192 parts of NH N(CH COONa) bythe procedure fE lIV, dth bt' clth d H(OCH2CHZ)8O(C3N3)[NHNKD ZCOO MZ oxamp e an ere 1s 0 am e compoun SO Na SO Na. compound, then there isadded 68 g. of ethylene diamine which also has marked fluorescentproperties. and the mixture refluxed for two hours. There is ob- EXAMPLEXXI tamed the compound A mixture of 141 parts of (NH (C N )(NHNH[(NaOOCCH NNH] (C N )NHCH CH NH 222 parts of ClCH COONa, and 80 parts ofNaOH dis- (C N [NHN(CH COONa) solved in 750 parts of water and refluxedfor one hour.

There is obtained a solution of the compound EXAMP XIX (NH (C N )NHN(CHCO0Na) Example XVII is repeated to prepare the 40 EXAMPLE XXII Theprocedure of Example II is repeated using 260 CMcaNs)[NHN(CH2COONa)2]2parts of (CH CHC H NH)(C N )Cl 240 parts of compound, and there is added43 g. of ethylene imine -N 2 2 5)2, and 80 P ts Of NaOH, and

and the mixture heated to 45 C. for 30 minutes, while there 15 obtamedthe Compound a dilute solution of NaOH is added to maintain neutrality.45 (cH CHC 1-1 )c There 1s obtained 1n solut1on the compound when 260parts of (cHzzcHcsHp) 3) 2 are used instead of the vinylanilidotriazinethere is obtained the compound Q F G 4 a s) z z p 2] 2 N(C N3)[NHN(CIICO 0Na)1]1 By these and related procedures such as given 1n I.A.C.S.,73, 2981-3008 (1951 J. Org. Chem, 24, 643 (1959 J. Org. Chem, 25, 202(1960), Macromoleculare Chemie, 37, 25 (1960), the compounds of thisinvention, shown in Table 1, can be readily prepared.

TABLE 1 T group Y ups o NHNC(H2COOH)z O -PO C2115 -POC2H5 O CzH5 O C2II5Same as above O 0 -PONa -PONa ONa OIwa Do. %0 %O -POCHzCI-I:CH2-lOCII2CH C1I 0CH1CE=OHZ 0C1I2C1I=GI1 OH OH -NHC12H25 N(C12H2s)2 (11 100011 (IIHCOOII (F1130 0011 NH(|JHCOOII 191101100011 NIICHC0O1I -NHzHN(CHzCOOH)z -NHCHzCH=CHz NHCH;CH=OH TABLE l.-Comtlm1ed '1 group Y groupsNH(CH2)GN(CH COOK) OCHzCHCHz -CHzCHCHz *NHN(CIIgCOOLl)z -NHCnH4CH2CHCHzNHC5H;CH:CHCH

-NH(CH2)gN(CH2COOH)2 -NH(CH2)2N(CHCO0H)2 NHCHS\H9H;

-NH(CHz)sN(CHzCOOH)g -NII(CH2)0N(CH2COOH)2 NHOH2sH9H CHzC O OH Same asabove -NIINHOCCH3 NHNHOCCH;

D0 NHNO C CaHs -NH1IIO C CaHs C6115 Ce s -NH(CH2)2N(CI-IzCOOCH-NHNHCaN3[N( 3)2]2 NHNHCaNa[N(CHa)2]2 NH(CHQ)2N(CHQCOOCHNHCHzCH2CaNa[N(C a)2l2 NH H2 H2C3N3[N(CH3)I The triazine compounds ofthis invention containing at least one T group wherein the -COOH groupis in the acid form, may be used in the acid form or they can be used inthe form of salts. The salts are readily obtained by reaction with basessuch as NaOH, LiOH, Ca(OH)2, Mg(OH) KOH, etc., or the correspondingoxides Where available such as CaO, MgO, etc., or the free acid may beconverted to ammonium salts by re- 0 action with ammonia and thesubstituted ammonias such as the amines, hydrazines, hydroxyl amines,etc., for example, ammonia, methyl amine, ethyl amine, dibutyl amine,ethanol amine, diethanol amine, triethanol amine, hydrazine, N-methylhydrazine, dimethyl hydrazine, phenyl hydrazine, ethylene diamine,diethylene triamine, phenylene diamine, pyridine, morpholine,piperazine, allyl amine, diallyl amine, propargyl amine, semicarbazide,guanidine, biguanidine, guanazole, trimethyl benzyl ammonium hydroxide,etc., as Well as bases such as triphenyl phosphine, tributyl stilbine,etc. For other purposes the T group can possess the carboxyl structurein the form of an ester which is then hydrolyzed by acids and bases toproduce the free acid or a salt, thus The new coordination compounds ofthis invention are readily prepared from the free acids of the newtriazines of this invention and the corresponding oxides of the metaldesired. However, they are more easily prepared by reacting a watersoluble or water dispersible salt of the triazine compound with a watersoluble metal derivative such as copper sulfate, nickel chloride, etc.

For example, when a solution of C N [NHN (CH COONa) is treated with asolution of CuSO a blue complex is formed which precipitates from thesolution, whereas when a solution of a cobalt salt is used, a red,insoluble precipitate is obtained. These dried precipitates do notchange color substantially on exposure to UV. light or when heated to C.for twenty-four to forty-eight hours. Also, when these metal salts arereacted with the compounds of Examples I to XVI inclusive, coordinationcomplexes are similarly obtained. Furthermore, when solutions of silver,cadmium, aluminum, chromium, iron, zinc, lead, titanium, uranium,zirconium, vanadium, uranium, palladium, lanthanum, mercury, nickel, andmanganese are used instead of copper and cobalt, coordination complexesare also obtained with the compounds of Examples I to XX inclusive.

EXAMPLE XXIII Parts (NH (C N )'NHNHCH COOH 20 Aqueous formaldehyde(37.2%) 32 are heated together under reflux at the boiling point of themixture for thirty minutes, yielding a condensation product that curesto an insoluble, infusible mass when a sample is heated on a hot plateat C. Instead of heating the reactants under reflux, as described above,the mixture can be shaken or stirred for a longer period, for example,twenty-four to seventy-two hours or longer at room temperature, toeffect reaction between the components and to obtain a soluble, fusiblereaction product which can be heat-hardened. This condensation is per-17 formed preferably in the presence of an alkaline condensationcatalyst, such as sodium hydroxide, sodium carbonate, ammonia,triethanolamine, hex'amethylene tetraamine, etc., and cured in thepresence of acidic curing catalyst, or catalysts which under theinfluence of the reaction or heat produce acidic substances, such asacetic acid, phthalic acid, ammonium phosphate, ammonium chloride,glycine, chloroacetamide, chloroacetyl urea, etc.

EXAMPLE XXIV Parts (NI-I (C N )NHNHCH COOH 40 Aqueous formaldehyde(37.2% CH O) 32 are heated together under reflux at the boiling point ofthe mixture, yielding a condensation product, a sample of which cures toan insoluble, infusible state when a sample is heated at 130-150 C. on ahot plate. The remainder of the solution is neutralized with 10% NaOH togive the sodium salt of the condensation product, a sample of which alsocures on the hot plate to an insoluble, infusible state at 130150 C. Tothe remainder of the solution is added 16 parts of CuSO in a 10% aqueoussolution, and there is obtained the copper coordination compound of theresin having the linkages which is bright-blue in color. A sample of thecopper derivative of the resin is also converted to the insoluble,infusible state by heating at 130-150 C.

Coordination compounds are also formed when cobalt, nickel, iron, zinc,and cadmium ions are added to the sodium salt of the condensationproduct.

EXAMPLE XXV Parts (CH NH) (C N )NHN(CH COONa) 62.6 Aqueous CH O (37.5%)24.0 NaOH in 10 parts H O 0.2

The above ingredients are refluxed for fifteen minutes to produce aresin dispersion which, when dehydrated, produces a clear, viscous resinand which, on heating to 140 C. becomes hard and infusible. In manycases, it is desirable to condense this and other triazines withmelamine and formaldehyde, or with urea and formaldehyde, phenol andaldehydes, etc., as shown in some of the subsequent examples.

When an equivalent amount of glyoxal is used in this example, fastercuring of the resin is obtained.

EXAMPLE XXVI Parts NH (C N [NI-IN(CH COOK) 54 Urea 54 Aqueous CH O(37.5% CH O) 130 The above ingredients are refluxed for twenty-fiveminutes to produce a clear syrup. On dehydration it cures slowly at 140C., but on the addition of 5 parts NH Cl, the cure is accelerated. Theaddition of 80 parts of alpha flock to the syrup produces a moldingcompound, which, after being dried at 70 C. has an excellent cure andgood flow when molded at 135 C. for four minutes. The product has aglossy surface and is light-colored. When an equivalent amount ofthiourea is substituted in the above formula, the type of cure, moldingcharacteristics, and appearance of the molded product obtained issubstantially the same as with that of urea.

EXAMPLE XXV II Parts Paratoluene sulfonamide 57 Aqueous CH O (37.5 CH O)190 18 The above ingredients are refluxed for one hour to produce asyrup which is clear while hot and cloudy on cooling.

EXAMPLE XXVIII Parts (NH (C N )NHN(CH COOLi) 142 Aqueous CH O (37.5% CHO) 190 Phenol 29 The above ingredients are refluxed for twenty-five tothirty minutes to give a clear syrup when hot. At 135 C. the syrup has aprolonged cure but when 7.5 parts of chloroacetamide are added to thecomposition, an excellent cure is obtained.

The above components are mixed and refluxed for fifteen minutes. Thesyrup does not cure well alone at 135 C., but the addition of 8 parts ofchloroacetamide accelerates the cure.

EXAMPLE XXXI (CH COONa) Aqueous CH O (37.5% CH O) 210 NH in 5 parts H O2 Aqueous trimethylol melamine (50% solu.) 130 When the aboveingredients are refluxed for twenty to thirty minutes a syrup isobtained which cures slowly alone. The cure is accelerated by ammoniumchloride to produce hard resins and molding compounds.

EXAMPLE XXXII Parts (NH (NH CONHNH) (C N )NHN (CH COOH) 130 Aqueous CH O(37.5 CH O) 130 Glycerine 10 The above mixture is refluxed fortwenty-five to thirty minutes to produce a clear resin curing at 140 C.,which cure is accelerated by the addition of curing agents.

EXAMPLE XXXIII Parts (NH C N )NHN(CH COOH) 125 Aqueous CH O (37.5% CH O)Butyl alcohol 100 These ingredients are mixed and refluxed for one-halfhour to produce a clear syrup which cures slowly at 135 C. After reflux,the water is removed from the reaction product by azeotroping themixture and returning the butyl alcohol to the reaction. The butylatedresin is reacted with heat-convertible alkyd resins for coatings andenamels of excellent color retention and durability.

19 EXAMPLE XXXIV Parts (NH C N NHN(CH COOH) 120 Aqueous CH O (37.5%CHQO) 150 Diethyl malonate 20 NaOH in 20 parts H O 2.5

are refluxed for twenty minutes to produce a condensation product whichcures at 140-160 C.

EXAMPLE XXXV Parts (NH (C N )NHN(CH COONa) 120 Aqueous CH O (37.5% CH O)140 NH in 5 parts H O 4.0 Acetamide 15.0

The above mixture is refluxed for fifteen minutes to produce a clearsyrup which cures alone at 135 C. With phthalic anhydride,chloroacetamide and ammonium chloride, respectively, the cure isaccelerated.

EXAMPLE XXXVI Parts Acrolein 38 NaOH in 5 parts H O 0.2

The reactants are mixed and refluxed for fifteen minutes to produce asyrup which cures at 140 C. to a hard tough resin by the addition ofammonium chloride.

EXAMPLE XXXVII Parts Shellac 50 HOOCCH NHNH-(C N )(NHCH OH) 15 Thedimethylol derivatives are prepared in accordance with the lowtemperature procedure of Example XXIII. The above components are mixedWell and fused at 150 C. At this temperature, the mixture cures to ahard, infusible resin. The addition of paraform and hexamethylenetetraamine, respectively, hastens the cure.

EXAMPLE XXXVIII Parts Alkyd resin (e.g. glyceryl phthalate) 50 HOOCCHNI-INH(C N (NHCH OH) 15 These components are mixed together and heatedon a hot plate at 150 C., and cures to a hard, infusible product. Thecuring is accelerated by paraform.

EXAMPLE XXXIX Parts l-phenyl guanazole 35 Aqueous formaldehyde (37.5 CHO) 35 Ammonia (28%) 2 Aqueous NaOH (0.5 N) 0.75 Reaction product ofExample XXIII 9 are heated together under reflux for five minutes at theend of which period separation of a resinous mass occurs. This resin isused satisfactorily for the production of molding compounds.

EXAMPLE XL Parts Soya bean protein 25 Aqueous ammonia (28% NH 2.5Aqueous NaOH (0.5 N) 3.0 Aqueous CH O (37.5% CH O) 150 (NH (C N )NHN(CHCOONH 80 are heated together under reflux at the boiling point of themixture for twenty minutes. The resin cures well when dehydrated andheated at 130 C.

EMMPLE XLI Parts Hz)2( 3N3)NHN(CH C0O) Mg 100 Aldol 100 are mixedtogether and then heated for forty hours at 60 C. The resinous materialthereby obtained melts on a hot plate at 140 C., and is converted to aninsoluble, infusible state by further heating.

EXAMPLE XLII The procedure of Example XXIV is repeated using 51.4 partsof and 64 parts of aqueous 37.5% CH O, and the resin dehydrated andtested. The dissociation constants, using the method given in J.A.C.S.74, 5052 (1952) as determined qualitatively are about k =4.5 10- and k=6.6 10- Separate samples of the condensation product are neutralizedwith NaOH, KOI-I, LiOH, CsOH, Ca(CH) Ba(OH) and Sr(OH) respectively, togive the corresponding salts of polymer products.

EXAMPLE XLIII The procedure of Example XXIV is repeated using 51.4 partsof (NH (C N )NHN(CH COOH) and 64 parts of aqueous 37.5% CH O andseparate samples of the condensation product is neutralized withammonia, hydrazine, N-methyl hydrazine, dimethyl hydrazine, methylamine, ethyl amine, butyl amine, diisopropyl amine, tributyl amine,ethylene diamine, diethylene triamine, ethanol amine, diethanol amine,triethanol amine, aniline, phenylene diamine, aminophenol, dimethylamine, pyridine, morpholine, polyethylene imine (MW 300), piperidine,hexamethylene diamine, tetramethylene diamine, allyl amine, andpropargyl amine and the corresponding salts are obtained.

EXAMPLE XLIV The procedure of Example XLII is repeated and the productof the condensation is poured into a glass tray and placed in an ovenheated to C. for twelve hours, followed by heating at C. for six hours.The product is crushed into granules of about 50 mesh and immersed in aSOO-part of a 5% solution of NaOH to form the sodium salt. The granulesare then washed with distilled water to remove mechanically-held NaOHand kept in a moist condition.

Twenty-five (25) parts of the Na salt of the resin are added to 100parts of solution containing 5 parts of CuCl and allowed to stand forone hour. The resin becomes blue in color and the copper becomessubstantially exhausted from the solution. Similar exhaustions areobtained when a 1% solution of CuCl in a 3% NaCl solution, or a 0.1%solution of CuCl in a 1% NaCl solution is used.

Recovery of copper is also obtained from solutions containing otheralkali and alkali-earth salts such as the salts of potassium, lithium,magnesium, calcium, strontium, such as their chlorides, nitrates,sulfates, phosphates, and acetates. For example, all of the copper isrecovered readily from a 15% calcium chloride solution having 25 p.p.m.of copper ion, as well as when the potassium, lithium, cesium, bariumand calcium salts of the coordination resin is used. Using the proceduredescribed by J. Bjerrum (Metal Amine Formation in Aqueous Solution,publisher Haase and Son, Copenhagen, 1941) it is determined that thepolymer forms both 1:1 and 1:2 chelates whose stability constants areapproximately K :5.75 10 and K =1.52 10 The polymer also formscoordinate compounds with ferric chloride corresponding to a 1:1, 1:2and 1:3 below pH values of about 8.5, and the stability constants ofthese compounds are "approximately about K =l.25 10 K =4.55 10" and K8.1 X 10 EXAMPLE XLV The procedure of Example XLIV is repeated with cobaltic chloride solutions and the metal is recovered in a 21 similarmanner. During the process the coordination polymer becomes red as itreacts with the cobalt ions.

When solutions of silver, cadmium, molybdenum, aluminum, cesium,lanthanum, chromium, manganous, manganic, ferrous, ferric, nickel, zinc,lead, platinum, palladium, vanadium, tantalum, zirconium, titanium, anduranium ions are used instead of the cobalt ions, they are alsorecovered in a similar fashion.

EXAMPLE XLVI Using the procedure of Example XLIV, coordinationderivatives are formed with the individual resins of Examples XXVII toXLI inclusive, with copper and the metal ions of Example XLV.

The aldehyde-amidogen polymers represent only one type of condensationpolymers that can be prepared from the new reactive triazine compoundsof this invention through condensation polymerization reactions. Bycondensation polymerization is meant an intermolecular reactioninvolving at least one of the triazines of this invention with at leastone related polyfunctional molecule, which as a result of inter-reactionliberates a by-product molecule. Condensation polymers, other than thealdehyde-amidogen polymers such as the polyester-, the polyamide-, thepolyalkylene-, the polyarylene-, etc., types are also readily preparedfrom the reactive triazine compounds of this invention; and, all ofthese polymers have, as a repeating unit, the same fundamental moiety,namely, a 1,3,5-triazine to which is attached at least one T group andthese polymers have the property of coordinating with metal ions, whichproperty is conferred to the polymer from the triazine compound fromwhich they are prepared.

Another modification of condensation polymerization is the reaction of apreformed polymer containing active hydrogens with the triazinecompounds of this invention, which contain functional or reactivegroups. Illustrative of such polymers are cellulose and cellulosederivatives, polyvinyl alcohol and its copolymers, polyacrylic andpolymethacrylic acid and its copolymers, polyacrylamide and itscopolymers, phenol-formaldehyde resins, polyethylene imines, etc.

These same characteristics, namely, (1) the property of coordinatingwith metal ions and (2) the existence, in the repeating unit, of thetriazinyl moiety to which is attached at least one T group, are alsofound in the addition polymers prepared from the reactive intermediatesof this invention.

By an addition polymerization is meant an intermolecular reactioninvolving at least a triazine of this invention which occurs without theformation of by-product molecules. The preparation of addition polymersfrom the new triazine compounds of this invention is readilydemonstrated by the polymerization of the new triazine derivatives whichhave at least one polymerization ethylenic group attached to thetriazine ring, such as illustrated by CH CHC H NH(C N )T (CH :CHC H NH)C N (T) 'CH CHCOOCH CH NH(C N )T 2C3N3 etc. These compounds are vinyltype monomers from which polymers may be prepared by methods well knownin the polymer art. They may be polymerized alone or with each other orwith other monomers to produce fusible or crosslinked polymers andcopolymers suitable for chelating resin use as well as for pigmentproduction. When the triazine monomer possesses only one CH =CH groupsuch as in CH =CHC H NH(C N )T and CHFCHCOOCH CH NH (C N )T thenthermoplastic polymers are obtained, Whereas when the triazine monomercontains at least two CH =CH groups then crosslinked polymers areobtained.

By copolymerizing a monovinyl triazine compound of this invention with adivinyl triazine compound, crosslinked copolymers are obtained. Suchcrosslinking can also be obtained by using a monovinyl triazine compoundwith another crosslinking agent which is not a triazine. Suchcrosslinking compounds can possess a multiplicity of vinyl, vinylene orvinylidene groups.

A few illustrative examples of crosslinking monomers, that is, monomershaving a multiplicity of vinyl, vinylene or vinylidene groups aredivinylbenzene, divinylnaphthalene, vinyl isopropenyl benzene, vinylallyl benzene, diisopropenyl benzene, diallyl benzene; thepolyunsaturated esters such as ethylene glycol diaciylate, ethyleneglycol dimethacrylate, trimethylene glycol dimethacrylate, diallylitaconate, glycol maleate, diallyl succinate, divinyl phthalate, diallylmaleate; the polyunsaturated ethers such as divinyl ether, trimethyleneglycol divinyl ether, hydroquinone divinyl ether, catechol divinylether, resorcinol divinyl ether, hydroquinone diallylether, catecholdiallyl ether, resorcinol diallyl ether; vinyl allylphenyl ether, vinylvinylphenyl ether, allyl vinylphenyl ether, vinyloxy-vinyl benzoate,vinyloxy-allyl benzoate, allyloxy allylbenzoate; the polyunsaturatedamides such as ethylene diacrylamide, ethylene dimethacrylamide,N-vinylacrylamide, N,N'-di vinylphthalic diamide,N,N'-diallylphthalamide, etc., and other polyunsaturated modifiers suchas vinyl phenylacrylate, Z-isopropenyl-S-acryloxynaphthalene,vinyl-3,5-diallyloxypalmitate, etc. The crosslinking monomers may beused alone or in conjunction With each other or with other monomershaving one vinyl, vinylene or vinylidene group such as vinyl chloride,vinylacetate, vinylpropionate, vinylbutyrate, vinylstearate,acrylonitrile, methacrylonitrile, vinylidene chloride, vinylene cyanide,-chloroacrylonitrile, acrylic acid, the acrylic esters such as themethyl, ethyl, propyl, butyl, etc. acrylates; methacrylic acid and itsesters such as the methyl, ethyl, propyl, butyl, heXyl, phenyl, etc.methacrylates; itaconic anhydride, itaconic acid and their monoanddi-esters, such as the methyl, ethyl, propyl, etc. esters; the acrylic,methacrylic, chloroacrylic and the cyanoacrylic amides, N-alkyl amides,N,N-dialkyl amides; the alkenylaryl compounds such as styrene, the monomethyl styrenes, the dimethyl styrenes, alphamethyl styrenes, the mono-,diand trichlorostyrenes, the o-, mand p-acetamido styrenes; vinylnaphthalene, vinyl carbazole, etc.; the alkenylaryl heterocycliccompounds such as vinyl pyridine, vinyl methyl pyridine, vinylquinoline; the diene- 1,3 compounds such as butadiene-l,3, isoprene2,3-dimethyl butadiene-l,3, chloroprene, 2-phenylbutadiene-1,3, methylvinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, N-vinylimidazole, the vinyl azlactones, the N-vinyl-Z-oxazolidinones, maleicanhydride, dimethyl maleate, etc.

These polymers and copolymers may be prepared in mass, in solution, insuspension and emulsion systems, using the accepted initiating systems,such as the per compounds which generate radicals, or thermally, or withultraviolet light or with ionizing radiation and in some cases withionic catalysts, both anionic and cationic, e.g., BF NaNH, BuLi, HF,etc.

The formation of other types of addition polymers from the triazines ofthis invention is illustrated further by the reaction through ringopening of triazine compounds containing at least one T groupand anothergroup containing the structure etc., or by the addition reaction of atriazine containing at least one T group and two NCO groups with anothercompound, including triazines which contain at least two activehydrogens such as diols, diamines, amino alcohols, etc., or by thereaction of a triazine having at least one T group and two other groupscontaining active hydrogens with a diisocyanate, etc.

Typical examples of other condensation polymerizations and a number ofaddition polymerizations within the scope of this invention areillustrated in the following examples.

EXAMPLE XLVII Example XVII is repeated to obtain the compound Cl(C N[NHN(CH COONa) then there is added 440 g. of polyvinyl alcohol (mol. wt.of about 4000) in 8000 parts of water and 40 g. of NaOH and the mixtureheated to 80l00 C. with stirring for about three hours. There isobtained a viscous aqueous dispersion of a polymer having one in tenhydroxyls converted to a cyanurate of the triazine compound of thegeneral formula which forms coordination compounds with copper ions andwith the metal ions of Example XLV.

EXAMPLE XLVIII Example XVII is repeated to prepare the compound Cl(C N)[NHN(CH COON21) then there is added for each mole of this compound 825parts of soda-cellulose (i.e. one mole of NaOH for each anhydroglucosideunit) in 8000 parts of water and the mixture heated at 7585 C. for fourhours, following which it is acidified with dilute hydrochloric acid andthere is obtained the triazinyl cellulose derivative having about 1 toglucoside units as a cyanurate of the general formula CHOH-CHOH whichforms coordination compounds similar to the polymer derivative ofExample XLVII.

EXAMPLE XLIX To 39.7 parts of (HOCH CH NH) C N NHN(CH COONa) in 400parts of Water in a reaction vessel equipped with a stirrer and heatingmeans, is added slowly with stirring at r 45-50 C. a solution of 20.1parts adipoyl chloride,

ClOC(CH COCl in 100 parts of carbon tetrachloride and there is obtainedthe polymer, after removal of water and CCl corresponding to thestructure OCH CII IIN-C CNHClI:C1IzOC(CHz)aCO L n J.

N N 1 NIlNlUU-gUUUlllg which exhibits coordination properties.

EXAMPLE L 24 EXAMPLE LI Forty-five and five-tenths parts (45.5) of(CGHSO 2C3N3NHN 2 and 6.0 parts of H NCH CH NH are refluxed in 200 partsof dioxane for eight hours, and then 20 parts of 36% aqueous HCl addedand the water and dioxane removed at 1.5 mm. pressure and the productwashed with water to remove sodium chloride and there is obtained apolymer having the structure Nrrmon c o 011 z 11 'EXAMPLE LII Theprocedure of Example LI is repeated using 10.8 parts of p-phenylenediamine instead of ethylene diamine and there is obtained a polymerhaving the structure in 500 parts of tetrahydrofuran is added one partof tributyl amine and the mixture refluxed for one hour and then thefurane removed at reduced pressure, leaving a polymer having therepeating unit,

EXAMPLE LIV Fifty parts of distilled water, 0.5 part of hydroxy apatite(0.005 to 0.2 micron size), 0.1 part of sodium dodecylbenzenesulfonate,0.1 part of benzoyl peroxide and 30 parts of are mixed in a suitablereaction vessel under deoxygenated nitrogen and stirred for twenty-eighthours at C., and the polymer is isolated by filtration, washed withalcohol and refluxed for twelve hours, with 500 parts of 10% alcoholicKOH, then neutralized with aqueous HCl to produce the polymer having thestructure CaLhNll 25 IEXAMPLE LV The procedure of Example LIV isrepeated using 30 parts of (CH CHCOOCH CH NH) C N NHCH CH N ('CH COOH)and there is obtained the cross-linked polymer having the repeating unitNHCHzCH NUJH COOEUz N -H HCO00GInO1-1 Nr1b EXAMPLE LVI Forty-nine partsof HOCH CH N (C N [NHCH CH N(CH COOH are heated in a reaction fiask innitrogen at 160 C. for four hours or until about two (2) parts of waterare eliminated. The reaction is then cooled and a crosslinked polyesterresin ha'ving coordination properties obtained having the repeatingstructure NHCH CH N(CH C O OH);

which exhibits coordination properties.

EXAMPLE LVII To a mixture of three parts of water, 2 parts of triethylamine, one part of glycerine and thirty parts of (HOCH CH NH) C N NHN(CH COONa 2 is added rapidly with vigorous stirring eighteen parts oftoluene diisocyanata and in a short time, foaming occurs and acrosslinked polyurethane having metal coordination properties isobtained.

While the invention has been described in relation to various specificembodiments thereof, it is understood that many substitutions and othermodifications thereof can be made within the scope and spirit of theinvention.

26 What is claimed is: 1. A symmetrical triazine having the structure,

and

wherein each of the symbols R R and R individually represents a radicalselected from the class of --H, 'CHR COOM, phenyl, cycloheptyl,cycl-ohexyl and an alkyl radical containing one to six carbon atoms andwherein at least one of the radicals represented by R R and R is -CHRCOOM, -M is a member consisting of hydrogen, quaternary ammonium groupand metals and R represents a member consisting of hydrogen, phenyl,cycloheptyl, cyclohexyl and an alkyl radical containing 1 to -6 carbonatoms, n represents an integer of 1 to 6, and Z represents a divalentaromatic hydrocarbon radical containing six to twelve carbon atoms.

2. A triazine of claim 1 in which at least one T group is -NHN(CH COOM)3. A triazine of claim 1 in which at least one T group is --NHCH CH N(CH CO OM 41. A triazine of claim 1 having the formula 2,328,961 9/1943DAlelio et a1. 260249.6 2,418,336 4/1947 DAlelio et a1. '26'0249.63,056,760 10/ 1962 DAlelio 260- 2496 XR JOHN M. FORD, Primary ExaminerUS. Cl. X.R.

